Slow Electron Transfer Rates for Fluorinated Cobalt Porphyrins:  Electronic and Conformational Factors Modulating Metalloporphyrin ET

2003 ◽  
Vol 42 (19) ◽  
pp. 6032-6040 ◽  
Author(s):  
Haoran Sun ◽  
Valeriy V. Smirnov ◽  
Stephen G. DiMagno
2022 ◽  
Author(s):  
A. William Rutherford ◽  
Andrea Fantuzzi ◽  
Dario Piano ◽  
Patrycja Haniewicz ◽  
Domenica Farci ◽  
...  

In thylakoid membranes, Photosystem II monomers from the stromal lamellae contain the subunits PsbS and Psb27 (PSIIm-S/27), while Photosystem II monomers from granal regions (PSIIm) lack these subunits. Here, we have isolated and characterised these two types of Photosystem II complexes. The PSIIm-S/27 showed enhanced fluorescence, the near-absence of oxygen evolution, as well as limited and slow electron transfer from QA to QB compared to the near-normal activities in the granal PSIIm. However, when bicarbonate was added to the PSIIm-S/27, water splitting and QA to QB electron transfer rates were comparable to those in granal PSIIm. The findings suggest that the binding of PsbS and/or Psb27 inhibits forward electron transfer and lowers the binding affinity for the bicarbonate. This can be rationalized in terms of the recently discovered photoprotection role played by bicarbonate binding via the redox tuning of the QA/QA?- couple, which controls the charge recombination route, and this limits chlorophyll triplet mediated 1O2 formation (Brinkert K et al. (2016) Proc Natl Acad Sci U S A. 113(43):12144-12149). These findings suggest that PSIIm-S/27 is an intermediate in the assembly of PSII in which PsbS and/or Psb27 restrict PSII activity while in transit, by using a bicarbonate-mediated switch and protective mechanism.


1979 ◽  
Vol 44 (5) ◽  
pp. 1540-1551 ◽  
Author(s):  
Jaro Komenda ◽  
Jiří Huzlík

Compounds of the type of 2-(4'-nitrobenzoyl)methylene-3-ethylbenzothiazoline (I) and 2-bis-(p-nitrobenzoyl)methylene-3-ethylbenzothiazoline (II) were studied polarographically and by ESR spectroscopy to obtain informations about their electrochemical and follow-up reactions and their conformation. Whereas with compounds of the type I the conjugation in their molecules is preserved, with type II the coplanarity of the molecules is disturbed, which is manifested in the values of the splitting constants of the ESR spectra and a slow electron transfer between both nitrophenyl substituents. These conclusions are supported by NMR spectroscopic studies.


2010 ◽  
Vol 44 (7) ◽  
pp. 2721-2727 ◽  
Author(s):  
Jeffrey S. McLean ◽  
Greg Wanger ◽  
Yuri A. Gorby ◽  
Martin Wainstein ◽  
Jeff McQuaid ◽  
...  

1992 ◽  
Vol 70 (6) ◽  
pp. 1833-1837 ◽  
Author(s):  
Yan Xiang ◽  
Gilles Villemure

The cyclic voltammograms of tris (2,2′-bipyridyl) iron(II) ([Fe(bpy)3]2+) adsorbed in clay-modified electrodes made from a range of different smectites were recorded. In all cases, at low scan speed (1 mV/s), the initial anodic peak current was much larger than the initial cathodic peak current. Partial reduction of the clay structural iron further increased the initial anodic to cathodic current ratio, suggesting that the discrepancy between the charge transferred in the anodic and cathodic scans was due to a slow electron transfer between the clay structural Fe(II) and the oxidized bipyridyl cations. However, no clear quantitative relation was found between the measured FeO contents of the different clays and the observed excess anodic currents. In fact, of all the clays tested only one, montmorillonite SWy-1, contained enough Fe(II) for it to account for all of the excess anodic charge transferred in the initial scan.


Author(s):  
EPHRAIM BUHKS ◽  
RALPH G. WILKINS ◽  
STEPHAN S. ISIED ◽  
JOHN F. ENDICOTT

1989 ◽  
pp. 131-140 ◽  
Author(s):  
G. McLendon ◽  
Q. Zhang ◽  
K. Pardue ◽  
F. Sherman ◽  
A. Corin ◽  
...  

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